EP0175638B1 - Heisshärtende Reaktionsharzmischung zur Imprägnierung von Isolierungen elektrischer Geräte und zur Herstellung von Formstoffen mit und ohne Einlagen - Google Patents
Heisshärtende Reaktionsharzmischung zur Imprägnierung von Isolierungen elektrischer Geräte und zur Herstellung von Formstoffen mit und ohne Einlagen Download PDFInfo
- Publication number
- EP0175638B1 EP0175638B1 EP85730113A EP85730113A EP0175638B1 EP 0175638 B1 EP0175638 B1 EP 0175638B1 EP 85730113 A EP85730113 A EP 85730113A EP 85730113 A EP85730113 A EP 85730113A EP 0175638 B1 EP0175638 B1 EP 0175638B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- resin mixture
- reaction resin
- hardening reaction
- accelerator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims description 8
- 238000009413 insulation Methods 0.000 title claims description 7
- 238000005470 impregnation Methods 0.000 title description 9
- 239000000654 additive Substances 0.000 title 1
- 238000013007 heat curing Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 229910015844 BCl3 Inorganic materials 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl styrenes Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229940052881 quinhydrone Drugs 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000012778 molding material Substances 0.000 abstract description 11
- 238000003878 thermal aging Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 8
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KFUSXMDYOPXKKT-VIFPVBQESA-N (2s)-2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OC[C@H]1OC1 KFUSXMDYOPXKKT-VIFPVBQESA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/637—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the in situ polymerisation of the compounds having carbon-to-carbon double bonds in a reaction mixture of saturated polymers and isocyanates
Definitions
- thermosetting reactive resin mixture for impregnating the insulation of electrical devices, formed from insulating sleeves of electrical conductors made of film or tape-shaped insulating materials, in particular of winding bars or coils of electrical machines, and for the production of molding materials with or without inserts, consisting of polyisocyanates and (Poly) epoxy resins, which are at least one olefinically unsaturated compound that contains no active hydrogen atoms, namely styrene or C 1 -C 4 alkyl styrenes or (meth) acrylic acid C 1 -Ca alkyl ester or diallyl phthalate or di- (meth) acrylic acid ester or mixtures of these compounds and which contain an accelerator system (catalyst).
- thermosetting reactive resin mixtures are known from DE-A 2 432 952, DE-A 2 308 802 and in particular DE-A 2 722 400.
- the proportion of the latter is 2 to 50% based on the polyisocyanate component.
- EP-A 35 072 discloses a thermosetting reaction resin mixture of polyisocyanates and polyepoxide resins which contains, as accelerators, addition complexes of tertiary amines and boron trichloride of the general formula BC1s ' NR 1 R 2 R 3 . Furthermore, an olefinically unsaturated compound, namely triallyl cyanurate (TAC), is added to this known reaction resin mixture as a crosslinking agent. This is provided in percentages by weight in the range from 0.5 to 10 percent by weight. Triallyl cyanurate has a structure with three terminal olefin groups.
- TAC triallyl cyanurate
- the third allyl group of the TAC does not take part in the reaction during crosslinking (see, for example, the article “Crosslinking of polyolefins in the presence of new s-triazines” by Ahne, Wiedenmann and Kleeberg in “Kautschuk + Kunststoffe “, 1975, pages 135 to 140). Rather, the third group is still detectable in the finished molding material and leads, particularly in the case of high TAC proportions, to a reduced stability of the polyolefin against thermooxidative degradation, ie to embrittlement.
- the TAC content is low, for example 1%, this is irrelevant for the reaction process during curing and the reaction proceeds chemically as if this low content of olefinically unsaturated compound (TAC) were not present at all. A pure polyaddition hardening then takes place. As a result, there are only properties for the cured end product that correspond to a cured polyisocyanate-epoxy resin mixture in which curing only results in the formation of cross-linked ring structures and linear structures.
- TAC olefinically unsaturated compound
- R 1 , R 2 and R 3 are identical or different aliphatic, aromatic, heterocyclic or arylaliphatic radicals and these radicals or two of them may also be bonded to one another in addition to the tertiary amine nitrogen atom; furthermore, the tertiary nitrogen atom can be built into a ring system which can also contain multiple compounds and can have an aromatic character, R i , R 2 , R 3 then representing a trivalent organic radical which has a C single and a C 1 Double compound is connected to the nitrogen.
- These accelerator systems have in the reaction resin mixture of polyisocyanate (poly) epoxy resin and at least one olefinically unsaturated compound such as styrene or C 1 -C 4 alkyl styrene or (meth) acrylic acid C 1 -Ca alkyl ester or diallyl phthalate or di (meth) acrylic acid ester or Mixtures of these compounds have a pronounced latency, ie the reaction resin mixture can be stored at room temperature for weeks without their very low viscosity values increasing. If suitable components are selected, the insulation sleeves can also be impregnated at room temperature, ensuring good soaking. Moldings can also be cast with or without inlays at room temperature.
- Gelling the invaded Re Action resin system takes place at temperatures of 70 to 140 ° C in an economically short time either outside the drinking bath or within it by means of current heating, and complete curing by means of current heating is also conceivable.
- the impregnated or cast objects can be brought into ovens for final hardening in any position, if necessary, without fear of the penetrating reaction resin mixture flowing out.
- this reactive resin mixture results in insulation or molding materials with high heat resistance and high long-term heat resistance, which can be used at high operating temperatures.
- polymerization inhibitors such as. B. quinhydrone, hydroquinone and hydroquinone monomethyl ether
- the storage stability of the mixtures can be increased again without the gel time of the system being prolonged at higher temperatures.
- BC1 3 adducts boron trichloride adducts
- BF s adducts boron trifluoride adducts
- latent accelerator effect of the BC1 3 adducts for isocyanate epoxy systems DE-PS 2655367
- BC1 3 amine complexes are also suitable for mixtures of polyisocyanate (poly) epoxy and an olefinically unsaturated compound which contains no active hydrogen atoms, or that the latent effect is even more so is more pronounced.
- the permanent heat resistance is increased by the addition of the olefinically unsaturated compounds without active hydrogen atoms, so that a further increase in the operating temperature is possible for the insulating materials and molding materials produced from the reaction resin mixture.
- the good shelf life of the reaction resin mixture is achieved if the reaction resin mixture contains 0.01 to 5 percent by weight of accelerator, based on the mixture of polyisocyanate (poly) epoxy-olefinically unsaturated compounds (without active hydrogens).
- the addition is 0.0001 to 2 percent by weight. It is preferred to choose 0.05 to 2.5 percent by weight for the accelerator and 0.01 to 0.05 percent by weight for the inhibitor in order to achieve trouble-free gelling at the higher temperatures.
- cycloaliphatic epoxides e.g. B. the 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexaxarboxylat, and heterocyclic epoxy compounds based on hydantoin, and monofunctional epoxies, such as phenylglycidyl ether, O-cresyl glycidyl ether, glycidyl ether etc. are used. Further epoxies are listed in the "Handbook of Epoxy Resin" by H. Lee and K. Neville (Mc. CRAW Hill Book Company, 1967). The use of very pure bisphenol A diglycidyl ether or very pure bisphenol F diglycidyl ether is particularly advantageous.
- the olefinic unsaturated compounds are those which have no hydrogen atoms reactive towards the NCO groups of the isocyanate, such as styrene, C 1 -C 4 alkylstyrenes, (meth) acrylic acid C 1 -C 8 alkyl esters, diallyl phthalate or di (meth ) Acrylic acid ester. Any mixtures of these compounds can also be used. Styrene and / or (meth) acrylic acid alkyl ester was preferably used.
- reaction complexes of tertiary amines and boron trichloride which are suitable as accelerator systems according to the invention can each have different properties which, under certain conditions, suggest the choice of one substance over the other.
- Proven accelerators are addition complexes of boron trichloride with tertiary amines in which R 1 and R 2 consist of identical radicals, preferably methyl groups and R 3 is an alkyl, aralkyl, aryl or heterocyclic radical.
- Complexes of pyridine or 1-substituted imidazoles are also particularly suitable.
- Addition complexes of boron trichloride with dimethyloctylamine have the advantage that they are easily soluble in the claimed mixtures.
- Typical polymerization inhibitor systems such as quinhydrone, hydroquinone, hydroquinone monomethyl ether, nitrobenzene, dinitrobenzene, dinitrochlorobenzene and other compounds which contain the free-radical polymerization of the olefinically unsaturated compound, which do not prevent active polymerization, do not come as polymerization inhibitors, which bring about a further increase in the shelf life of the claimed reaction resin mixture .
- the reaction resin mixtures according to the invention can also contain inorganic mineral fillers for the production of molding materials.
- Typical fillers are quartz powder, aluminum oxide or chalk.
- Test rods consisting of flat rods made of copper, wrapped with four layers of polyimide film half-overlapped on one side and a cover layer made of a glass fabric, were impregnated with a mixture according to test 4 (example 2) at room temperature in vacuo.
- the viscosity of the reaction resin mixture before the impregnation was 7 mPas / 23.5 ° C.
- the test winding was placed in a heating oven at 130 ° C.
- three large standard bars without inlays and a plate 200 mm x 200 mm x 3 mm were cast as molding materials.
- the molded materials have the following mechanical properties:
- the molded materials have the following properties:
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Reinforced Plastic Materials (AREA)
- Organic Insulating Materials (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Stereophonic System (AREA)
- Epoxy Resins (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85730113T ATE47930T1 (de) | 1984-09-14 | 1985-08-27 | Heisshaertende reaktionsharzmischung zur impraegnierung von isolierungen elektrischer geraete und zur herstellung von formstoffen mit und ohne einlagen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3434270 | 1984-09-14 | ||
| DE19843434270 DE3434270A1 (de) | 1984-09-14 | 1984-09-14 | Heisshaertende reaktionsharzmischung zur impraegnierung von isolierungen elektrischer geraete und zur herstellung von formstoffen mit und ohne einlagen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0175638A1 EP0175638A1 (de) | 1986-03-26 |
| EP0175638B1 true EP0175638B1 (de) | 1989-11-08 |
Family
ID=6245714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85730113A Expired EP0175638B1 (de) | 1984-09-14 | 1985-08-27 | Heisshärtende Reaktionsharzmischung zur Imprägnierung von Isolierungen elektrischer Geräte und zur Herstellung von Formstoffen mit und ohne Einlagen |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4636556A (es) |
| EP (1) | EP0175638B1 (es) |
| JP (1) | JPS6178814A (es) |
| AT (1) | ATE47930T1 (es) |
| BR (1) | BR8504431A (es) |
| DE (2) | DE3434270A1 (es) |
| ES (1) | ES8700487A1 (es) |
| FI (1) | FI85154C (es) |
| GR (1) | GR852212B (es) |
| IN (1) | IN164366B (es) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3807660A1 (de) * | 1988-03-09 | 1989-09-21 | Bayer Ag | Lagerstabile reaktionsharzmischung, herstellung und verwendung |
| FR2636636B1 (fr) * | 1988-09-16 | 1992-09-04 | Alsthom Gec | Melanges stables a temperature ambiante de resines reactives thermodurcissables, complexes catalyseurs latents de durcissement de ces melanges, leurs procedes de fabrication et resines thermodurcies obtenues a partir de ces melanges |
| DE669960T1 (de) * | 1992-11-20 | 1996-02-29 | The Dow Chemical Co., Midland, Mich. | Verbesserte hochtemperaturstabilitätaufweisende polyharnstoffpolymere sowie verfahren zu deren herstellung. |
| CA2197961A1 (en) * | 1996-02-29 | 1997-08-29 | Michael D. Gammage | Introducer system having smooth transition of dilator and sheath |
| DE19811333A1 (de) * | 1998-03-16 | 1999-09-23 | Herberts Gmbh | Für metallische Leiter geeignete Beschichtungszusammensetzung |
| DE102017008925A1 (de) * | 2017-09-25 | 2019-03-28 | Hexion GmbH | Imprägnierharzmischung |
| CN111757899B (zh) * | 2018-02-22 | 2023-01-17 | 巴斯夫欧洲公司 | 对热变形和撕裂伸长率具有优异耐受性的基于聚氨酯的聚合物材料 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317048A (en) * | 1970-08-11 | 1973-05-16 | Ciba Geigy Uk Ltd | Curable epoxide resin compositions |
| US3836492A (en) * | 1970-12-24 | 1974-09-17 | Kansai Paint Co Ltd | Polymerizable unsaturated reaction product of a diisocyanate and an unsaturated product of a dicarboxylic acid anhydride and an unsaturated monoglycidyl monomer |
| BE795448A (nl) * | 1972-02-24 | 1973-08-16 | Shell Int Research | Werkwijze voor de bereiding van hardbare composities |
| GB1474371A (en) * | 1973-07-11 | 1977-05-25 | Shell Int Research | Copolymerization process |
| US4022721A (en) * | 1974-09-26 | 1977-05-10 | Mitsubishi Chemical Industries Ltd. | Process for producing compounds having an oxazolidone ring using a complex of aluminum halide catalyst |
| JPS5356294A (en) * | 1976-10-30 | 1978-05-22 | Hitachi Chem Co Ltd | Thermosetting resin composition |
| DE2655367C2 (de) * | 1976-12-03 | 1978-12-07 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Heißhärtende Reaktionsharzmischung zur Imprägnierung von Isolierungen elektrischer Geräte und zur Herstellung von Formstoffen mit oder ohne Einlagen |
| DE2722400C2 (de) * | 1977-05-17 | 1985-05-30 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von wärmebeständigen, blasenfreien Isocyanuratgruppen aufweisenden Kunststoffen |
| CH624968A5 (es) * | 1977-06-14 | 1981-08-31 | Ciba Geigy Ag | |
| US4224422A (en) * | 1979-06-28 | 1980-09-23 | Minnesota Mining And Manufacturing Company | Modified epoxy resin-polyisocyanate resin system |
| US4225460A (en) * | 1979-06-28 | 1980-09-30 | Minnesota Mining And Manufacturing Company | Latent Lewis acid catalyst system and process |
| DE3068153D1 (en) * | 1980-03-03 | 1984-07-19 | Bbc Brown Boveri & Cie | Duroplastically hardenable resin mixture free of solvents, and its use |
-
1984
- 1984-09-14 DE DE19843434270 patent/DE3434270A1/de not_active Withdrawn
-
1985
- 1985-08-27 EP EP85730113A patent/EP0175638B1/de not_active Expired
- 1985-08-27 DE DE8585730113T patent/DE3574196D1/de not_active Expired
- 1985-08-27 AT AT85730113T patent/ATE47930T1/de not_active IP Right Cessation
- 1985-09-10 US US06/774,310 patent/US4636556A/en not_active Expired - Fee Related
- 1985-09-10 JP JP60200399A patent/JPS6178814A/ja active Granted
- 1985-09-11 IN IN645/CAL/85A patent/IN164366B/en unknown
- 1985-09-12 GR GR852212A patent/GR852212B/el unknown
- 1985-09-13 ES ES546954A patent/ES8700487A1/es not_active Expired
- 1985-09-13 BR BR8504431A patent/BR8504431A/pt not_active IP Right Cessation
- 1985-09-13 FI FI853510A patent/FI85154C/fi not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE47930T1 (de) | 1989-11-15 |
| US4636556A (en) | 1987-01-13 |
| BR8504431A (pt) | 1986-07-15 |
| JPH032447B2 (es) | 1991-01-16 |
| DE3434270A1 (de) | 1986-03-20 |
| GR852212B (es) | 1986-01-11 |
| EP0175638A1 (de) | 1986-03-26 |
| JPS6178814A (ja) | 1986-04-22 |
| FI853510L (fi) | 1986-03-15 |
| FI85154B (fi) | 1991-11-29 |
| ES546954A0 (es) | 1986-10-16 |
| DE3574196D1 (en) | 1989-12-14 |
| FI85154C (fi) | 1992-03-10 |
| ES8700487A1 (es) | 1986-10-16 |
| IN164366B (es) | 1989-03-04 |
| FI853510A0 (fi) | 1985-09-13 |
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